Bis-anilide compositions as algicidal agents

ABSTRACT

This invention relates to the utility of certain bis-anilide compositions of the general formula:   WHEREIN R is alkyl having from 2 to 7 carbon atoms, inclusive, and R&#39;&#39; is selected from the group consisting of benzyl, 3,4dichlorophenyl, 2,4-dichlorophenyl, 2,4-dichlorophenoxymethyl, 1isobutenyl, alkyl having from 2 to 7 carbon atoms, inclusive, and haloalkyl having 1 to 2 carbon atoms, inclusive, as algicidal agents.

United States Patent [191 Baker et al.

[ Apr. 29, 1975 BIS-ANILIDE COMPOSITIONS AS ALGICIDAL AGENTS [75]Inventors: Don R. Baker, Orinda; Eugene G.

Teach, El Cerrito, both of Calif.; Duane R. Arneklev, Antelope, Mont.

[73] Assignee: Stauffer Chemical Company,

Westport, Conn.

[22] Filed: Apr. 9, 1973 [21] Appl. No.: 349,342

Related U.S. Application Data [63] Continuation-impart of Ser. No. l9845(), Nov. 12,

1971. abandoned.

Primary E.\'aminerLewis Gotts Assistant E.\'aminerCatherine L. MillsAttorney, Agent, or Firm-Harry A. Pacini; Daniel C. Block; Edwin H.Baker [57] ABSTRACT This invention relates to the utility of certainbisanilide compositions of the general formula:

wherein R is alkyl having from 2 to 7 carbon atoms, inclusive, and R isselected from the group consisting of benzyl, 3,4-dichlorophenyl,2,4-dichlorophenyl. 2,4dichlorophenoxymethyl, l-isobutenyl, alkyl havingfrom 2 to 7 carbon atoms, inclusive, and haloalkyl having I to 2 carbonatoms, inclusive, as algicidal agents.

29 Claims, No Drawings BIS-ANILIDE COMPOSITIONS AS ALGICIDAL AGENTS Thisapplication is a continuation-in-part of copending application Ser. No.198,450, filed Nov. 12. 1971 now abandoned.

This invention relates to the utility as algicidal agents for thecontrol of algae when used in an algicidally effective amount of certainsubstituted bis-anilides of the general formula:

9 bIIHC-R wherein R is alkyl having from 2 to 7 carbon atoms, inelusive,and R is selected from the group consisting of benzyl,3,4-dichlorophenyl, 2,4-dichlorophenyl, 2,4- dichlorophenoxymethyl,l-isobutenyl, alkyl having from 2 to 7 carbon atoms, inclusive, andhaloalkyl having 1 to 2 carbon atoms, inclusive. It was found that thesecompounds have an algicidal property and provide beneficial results incontrolling the growth of algae.

Controlling the growth of algae by employing the compounds describedherein can be accomplished by applying an aligicidally effective amountto the environment in which algae growth is normally encouraged. Thecompounds may be applied to any environmental area which is a host toalgae or susceptible to algae attack and growth. By controlling, it ismeant the inhibition, eradication or elimination, and prevention of thegrowth of the organism to be controlled.

The term alkyl as used herein, i.e., both in the specification andclaims, contemplates linear and branched chain alkyl radicals containingfrom 2 to 7 carbon atoms, inclusive, such as ethyl, n-propyl, isopropyl,nbutyl, iso-butyl, sec.-butyl, tert.-butyl, n-amyl, isoamyl, n-hexyl,l,l-dimethylbutyl, and the like. The term haloalkyl as used hereincontemplates halogen substituted alkyl radicals containing from 1 to 2carbon atoms, inclusive, such as monochloromethyl, dichloromethyl,trichloromethyl, monochloroethyl, dichloroethyl, trichloroethyl,pentachloroethyl, bromomethyl,

.bromoethyl, iodomethyl, iodoethyl, trifluoromethyl,

pentafluoroethyl, chlorofluoromethyl, chlorofluoroethyl,monofluorotetrachloroethyl, and the like.

The following compounds in Table I can be used, for example, accordingto the invention hereindescribed. Compound numbers have been assignedand are used throughout the balance of this application.

TABLE 1 ll NHC-R PHYSICAL COMPOUND CONSTANT NUMBER R V R' I'D-E. c.

g 1. c 11 001 159-161 2 c 11 CF3 196 197 3 i-C H cc1 -162 s c11(c11 )c Hca(c11 )c 11 111-115 9 C(CH3)3 3,4-di-C1-phenyl 187-191 10 c (c11 c 11 2idi-Cl-pheny1 153-157 11 T c(c1+1 c 11 011 0-2 ,4-di-Cl-phenyl 126 -12912 0 11 I c11 c(c11 3 177-179 TABLE 1-Continued ll NHC-R PHYSICALCOMPOUND CONSTANT NUMBER R R v1. c.

l3 0 H 3,4-di-Cl-phenyl 175-177 14 C l-l CC1 CH 16 3-165 The compoundsmentioned thus far, and those contemplated, can be prepared, forexample, according to the following methods.

The compounds herein disclosed are prepared by one of several generalmethods. One such general method is the condensation between theappropriate mphenylene diamine and an appropriate acid anhydride or acidchloride to prepare the desired meta-bis-symmetrically substitutedanilide. Another general method is the condensation between theappropriate m-monosubstituted amino anilide and an appropriate acidanhydride or acid chloride to prepare the desiredmeta-bis-assymetrically substituted anilide. The reactions proceedreadily in the liquid phase. The employment of a solvent is also useful,facilitating processing, as well as agitation of the reactants. Whenusing a starting material containing an acid chloride, it is preferredto carry out the reaction in the presence of a hydrogen halide acceptorsuch as triethylamine, pyridine, picoline, sodium carbonate and thelike. The reactions are preferably carried out at temperatures thatpermit operation in the liquid phase. Upon completion of the reaction,normal work-up procedures are applicable to recover the purifiedcompound, such as, solvent extraction, crystallization, distillation andthe like.

The following illustrated examples describe in detail,

without restriction thereto, the preparation of several representativecompounds.

EXAMPLE I Preparation of 3'-trichloroacetamido propionanilide.

ered by filtration and washed consecutively with dilute hydrochloricacid and water. The product was dried in a vacuum oven. There wasobtained 15.3 g. of the title product, m.p. 159-161C.

EXAMPLE ll 1 Preparation of 3 2 ,2-dimethylvaleramido)-t-butyl-acetanilide.

ALGlCIDAL TEST PROCEDURE Sufficient candidate toxicant is diluted inacetone to give an 0.5 percent mixture which is then diluted into 20milliliters of warm modified Jack Meyers Agar Medium (Algae Culture fromLaboratory to Pilot Plant", 1953, Page 94). The dilutions of the testcompounds are selected concentrations of' from 0.5 to 50 #g/ml.including 1.0, 5.0 and 10.0 pg/ml. The selected concentrations aretested in 20 X mm. Petri dishes. After the agar solidifies, separatePetri dishes are innoculated with the desired organism, suchasScenedesmus obliquus or Chlorella pyrenoidosa. The innoculated samplesare then allowed to grow at room temperature under fluorescent lampsusing a 14 hour light period each day. After one to two weeks, dependingupon the growth of the untreated controls, the results are recorded asto the level necessary to control the specific organism. The resultsobtained with representative compounds and their concentrations aregiven in Table II. i

TABLE II ALGlClDE TEST COM- (concentration, (concentration, POUND NUMBERug/ml.) fl-g/ml.)

I 1 .0* 0.5 2 1.0* (0.5) 3 1 .0* 0.5 4 I .0* L 5 1 .0* L0) 6 1 .0* 0.5 71 e 0.5 8 I .0* 1.0 9 1 .0* 0.5 10 1 .0* 1.0 l l 1 .0* 0.5 l2 5.0 (5.0)13 50 1.0 [4 (5.0) (L0) 15 5.() 1.0) 16 50 (50) 17 50.() 50.0 18 50 1.0I) 50.0 1.0) 20 500 (50.0) 2] 500 (5.0) 22 50.0 5.0 23 (50.0) (5.0) 24(50.0) 50.0 25 50.0 5.0 26 50.0 5.0 27 (50.0) L0 28 50.0 L0 29 (5.0) 1.030 (5.0) L0 denotes partial control at the indicated concentrationdenotes not tested denotes highest concentration tested The manner inwhich the water area may be treated for the control of algae will varywith the specific problems encountered. An acute problem in the storageand utilization of industrial process water is the fouling of such waterand systems in which the water is used by the growth of algae. Entireareas such as a pond or lake may be treated. Drainage ditches and otherwaterflowing sites may be treated.

In addition to use in ponds and lakes, this invention is applicable tothe control of algae in industrial cooling towers and other waterrecirculating systems as used in paper manufacturing processes, forexample.

The substances to be employed according to the present invention can beused as such or in the form of formulations with carrier vehicles.Examples and emulsifiable concentrates, spray powders, pastes, solublepowders, and the like. Suitable carrier vehicles or assistants aremainly: Solvents, such as, optionally chlorina ted, aromatichydrocarbons (e.g., xylene, benzene, chlorobenzenes), paraffins (e.g.,petroleum fractions), alcohols (e.g., methanol, ethanol, butanol),amines (e.g., ethanolamine, dimethyl formamide), as well as water;finely divided solid carriers, for example, natural and synthetic stonemeals or powders (kaolin, alumina, chalk, i.e., calcium carbonate, talc,highly disperse silicic acid, silicates, e.g., alkali silicates);emulsifiers, such as non-ionic and anionic emulsifiers (e.g.,polyoxyethylene fatty acid esters and polyoxyethylene fatty alcoholethers, alkyl sulfonates and aryl sulfonates) especially magnesiumstearate, sodium oleate, etc., and

dispersing agents such as lignin, sulfite waste liquors and methylcellulose.

As already mentioned above, the active compounds or agents to beemployed according to the instant invention can be present in theaforesaid formulations in mixture with one another and with other knownactive substances.

The algicidal compositions of the invention also comprise aqueousemulsions. The aqueous emulsions can be prepared by dissolving asurfactant of the type noted hereinabove and pouring the emulsifiableconcentrate so obtained into water with vigorous agitation. The aqueousemulsions of the invention can also be prepared by dissolving the activeingredient in a watermiscible solvent such as Carbitol (diethyleneglycol monoethyl ether), acetone, a lower alkanol, Cellosolve (ethyleneglycol monoethyl ether), dioxan, and the like, if desired, inassociation with a surfactant such as noted above, to obtain anemulsifiable concentrate which is poured into water with vigorousagitation. The aqueous emulsions of the invention can also be preparedby dissolving the active ingredient and a surfactant such as noted abovein an organic solvent which is immiscible with water. The resultingemulsifiable concentrate is then admixed with water with vigorousagitation to form an emulsion. The water-immiscible organic solventswhich are suitable for use include cyclohexanone, summer oils, aromatichydrocarbons such as benzene, toluene, xylene, and high-boilingpetroleum hydrocarbons such as kerosene, diesel oil, and the like.

The aqueous emulsions of the invention can be supplied to the user inthe form of the emulsifiable concentrates described above which requiredilution with water before use. Both the concentrated compositions andthe diluted compositions are included within the scope of the presentinvention.

Formulations contain, in accordance with the present invention, ingeneral from 0.1 to 95, preferably 0.5 to 90, per cent by weight ofactive compound or agent. The agents according to the present inventionor their preparations are applied in the usual way, e.g., by spraying,dusting, sprinkling or atomizing. The active substances can be applied,according to the purpose in view, in a concentration of 5 to 0.0005percent. In special cases it is, however, possible or even necessary togo below or above these concentrations. The remainder of activealgicidal composition being an adjuvant which can be a liquid extendingagent or surfact active agent, but preferably is an admixture thereof.

Various changes and modifications are possible without departing fromthe spirit and scope of the invention described herein and will beapparent to those skilled in the art to which it pertains.

What is claimed is:

l. The method for inhibiting and preventing algae growth in water, whichcomprises adding to the algae environment an algicidally effectiveamount of a compound of the formula NHC -R wherein R is alkyl havingfrom 2 to 7 carbon atoms, inclusive and R is selected from the groupconsisting of benzyl, 3,4-dichlorophenyl, 2,4-dichlorophenyl, 2,4-dichlorophenoxymethyl, l-isobutenyl, alkyl having from 2 to 7 carbonatoms. inclusive, and haloalkyl having 1 to 2 carbon atoms, inclusive.

2. The method according to claim 1 in which R is alkyl and R is alkyl.

3. The method according to claim 2 in which R is 1.1- dimethylbutyl andR is neopentyl.

4. The method according to claim 2 in which R is 3- methylbutyl and R isl,l-dimethylbutyl.

5. The method according to claim 2 in which R is ethyl and R isneopentyl.

6. The method according to claim 2 in which R is lmethylbutyl and R istertiary-butyl.

.7. The method according to claim 2 in which R is ethyl and R isl-ethylpentyl.

8. The method according to claim 2 in which R is lmethylbutyl and R isl-methylbutyl.

9. The method according to claim 1 in which R is alkyl and Rishaloalkyl.

10. The method according to claim 9 in which R is ethyl and R istrichloromethyl.

11. The method according to claim 9 in which R is ethyl and R istrifluoromethyl.

12. The method acccording to claim 9 in which R is isopropyl and R istrichloromethyl.

13.. The method according to claim 9 in which R is ethyl and R isl,l-dichloroethyl.

14'. The method according to claim 9 in which R is l, l-dimethylbutyland R is trifluoromethyl.

16. The method according to claim 9 in which R is I ethyl and R isl,l-dichloro-2,2.2-trifluoroethyl.

17. The method according to claim 9 in which R is 1.1-dimethylbutyl andR is pentafluoroethyl.

18. The method according to claim 1 in which R is alkyl and R is benzyl.

19. The method according to claim 18 in which R is l-methylbutyl.

20. The method according to claim 18 in which R is 1,1-dimethylbutyl.

21. The method according to claim 1 in which R is alkyl and R is3,4-dichlorophenyl.

22. The method according to claim 21 in which R is tertiary-butyl.

23. The method according to claim 21 in which R is ethyl.

24. The method according to claim 1 in which R is alkyl and R is2,4-dichlorophenyl.

25. The method according to claim 24 in which R is l, l -dimethylbutyl.

26. The method according to claim 1 in which R is alkyl and R is2,4-dichlorophenoxymethyl.

27. The method according to claim 26 in which R is l,l-dimethylbutyl.

28. The method according to claim 1 in which R is alkyl and R isl-isobutenyl.

29. The method according to claim 28 in which R is tertiary-butyl.

1 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION d PATENT NO.3,880,642

DATED 1 April 29, 1975 |NVENTOR(S) Don R. Baker et a1.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below: 0

In printing the patent, the following portion of Table I was omitted:

PHYSICAL COMPOUND CONSTANT NUMBER 3 R' m. c.

22 CH(CH C H C(CH C H glass 23 CH CH(CH )C H C H 123-126 28 CH(CH )C H 0F 126-128 29 C(CH C H C 1 112-114 a Signed and Sealed this Twenty-eighthDay or December 1976 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner oflatenrsand Trademarks

1. THE METHOD FOR INHIBITING AND PREVENTING ALGAE GROWTH IN WATER, WHICHCOMPRISES ADDING TO THE ALGAE ENVIROMENT AN ALGICIDALLY EFFECTIVE AMOUNTOF A COMPOUND OF THE FORMULA
 2. The method according to claim 1 in whichR is alkyl and R'' is alkyl.
 3. The method according to claim 2 in whichR is 1,1-dimethylbutyl and R'' is neopentyl.
 4. The method according toclaim 2 in which R is 3-methylbutyl and R'' is 1,1-dimethylbutyl.
 5. Themethod according to claim 2 in which R is ethyl and R'' is neopentyl. 6.The method according to claim 2 in which R is 1-methylbutyl and R'' istertiary-butyl.
 7. The method according to claim 2 in which R is ethyland R'' is 1-ethylpentyl.
 8. The method according to claim 2 in which Ris 1-methylbutyl and R'' is 1-methylbutyl.
 9. The method according toclaim 1 in which R is alkyl and R'' is haloalkyl.
 10. The methodaccording to claim 9 in which R is ethyl and R'' is trichloromethyl. 11.The method according to claim 9 in which R is ethyl and R'' istrifluoromethyl.
 12. The method acccording to claim 9 in which R isisopropyl and R'' is trichloromethyl.
 13. The method according to claim9 in which R is ethyl and R'' is 1,1-dichloroethyl.
 14. The methodaccording to claim 9 in which R is 1,1-dimethylbutyl and R'' istrifluoromethyl.
 15. The method according to claim 9 in which R istertiary-butyl and R'' is pentafluoroethyl.
 16. The method according toclaim 9 in which R is ethyl and R'' is1,1-dichloro-2,2,2-trifluoroethyl.
 17. The method according to claim 9in which R is 1,1-dimethylbutyl and R'' is pentafluoroethyl.
 18. Themethod according to claim 1 in which R is alkyl and R'' is benzyl. 19.The method according to claim 18 in which R is 1-methylbutyl.
 20. Themethod according to claim 18 in which R is 1,1-dimethylbutyl.
 21. Themethod according to claim 1 in which R is alkyl and R'' is3,4-dichlorophenyl.
 22. The method according to claim 21 in which R istertiary-butyl.
 23. The method according to claim 21 in which R isethyl.
 24. The method according to claim 1 in which R is alkyl and R''is 2,4-dichlorophenyl.
 25. The method according to claim 24 in which Ris 1,1-dimethylbutyl.
 26. The method according to claim 1 in which R isalkyl and R'' is 2,4-dichlorophenoxymethyl.
 27. The method according toclaim 26 in which R is 1,1-dimethylbutyl.
 28. The method according toclaim 1 in which R is alkyl and R'' is 1-isobutenyl.
 29. The methodaccording to claim 28 in which R is tertiary-butyl.